Plant hormone carboxylic acid salts of aliphatic polyamines

ABSTRACT

Plant hormone carboxylic acid salts of aliphatic polyamines having at least six carbon atoms in an aliphatic radical thereof, useful as herbicidal agents.

United States Patent 151 3,683,010 Reck et al. 1451 Aug. 8, 1972 [54]PLANT HORMONE CARBOXYLIC 347.3, 260/5012, 501.16, 404.5; 71/1 13-1 17ACID SALTS OF ALIPHATIC POLYAMINES 56 f 72 Inventors: Richard A.Reck,l-1insdale; Walter 1 CM W. Abramitis,'Downers Grove, both UNITEDSTATES PATENTS 3,206,485 9/1965 Pflaumer ..260/50l.16 [73] Assignee:Armour Industrial Chemical Com- 2,900,411 8/1959 Harwood et al. ..7l/2.6

22 H d 26 1966 FOREIGN PATENTS OR APPLICATIONS 1 1,402,696 7/1964 France[211 App]. No.: 581,725

Primary Examiner-Leon Zitver Rem! Apphcauon Data Assistant ExaminerM. W.Glynn [63] Continuation-impart of Ser. No. 300,108, Aug. Attrney-Francis W- Young 5, 1963, abandoned.

[57] ABSTRACT [52] U.S. Cl. .....260/50l .l6, 260/5012, 260/50Ll7, Hamhormone carboxylic acid salts of aliphatic 260/326'13 260/3473 71/9671/88 polyamines having at least six carbon atoms in an [5 n In (:1.I?!111111.1113131120115113 a'iphafic 1911991996, as he'bicida' [58]Field of Search...260/501 N, 501 W, 326.13, 5 Claims, No Drawings PLANTHORMONE CARBOXYLIC ACID SALTS OF ALIPHATIC POLYAMINES This applicationis a continuation-in-part of copending application Ser. No. 300,108,filed Aug. 5, 1963, now abandoned.

Plant hormone carboxylic acids are believed to kill certain vegetationby stimulating the plants to excessive growth while having no unusualstimulating efi'ect upon other vegetation. The use of such acids withother compounds, including aliphatic amines, has been'found effective incontrolling many types of weeds and other plants. One difficulty,however, has been the tendency for the product to volatilize in aircurrents and to be applied to plants which are not intended to bedestroyed. For example, it is common to apply the herbicide compositionalongside roadways and adjoining crops, such as cotton, vegetableplants, etc., which must be protected from the action of thecomposition. Unfortunately, the herbicide composition can becomeairborne under the circumstances of spraying or other application, andserious damage to the beneficial plants is caused.

We have discovered that by reacting a polyamine having at least sixcarbon atoms in an aliphatic radical with a plant hormone carboxylicacid, thus forming a salt, a highly effective herbicide, havingsubstantially no tendency to volatilize in air currents, is obtained,thus permitting the composition to be sprayed all about a plant todestroy the weeds, etc., without injury to the plant. Not only does thecomposition become nonvolatile so that it can be safely applied byspraying along a marginal area without danger of drifting, but also thecomposition has enhanced weed-killing values in providing better rootpenetration and slow-acting destruction.

A primary object of the invention, therefore, is to provide planthormone carboxylic acid salts of higher aliphatic diamines which producethe above-described new results. A further object is to provide diamineor polyamine salts of herbicidal acids which are oil-soluble and whichmay be dispensed in oil-and-water emulsions, and which provide a heaviermolecule composition having little tendency to drift with air currentswhen applied by spraying. A still further object is to provide a diaminesalt herbicidal composition having unique properties enabling it to beapplied around plants for the destruction of weeds but without injuringthe plant. Other specific objects and advantages will appear as thespecification proceeds.

In one embodiment of our invention, an aliphatic diamine havingpreferably from six to 23 carbon atoms in a aliphatic radical thereof isreacted with a plant hormone carboxylic acid to form a salt of the twosubstances. The resulting composition is oil soluble and can be appliedin organic solvents, such as kerosene, xylene, aromatic oils, acetone,diacetone, isopropanol, etc. If desired, an oil-in-water emulsion may beformed and the composition applied in such an emulsion. The applicationcan be by spraying and, by way of specific example, it can be statedthat the spray can be applied about a peony bush for destroying theweeds about the thereof. A representative formula of preferred diaminesis RNHCl-I CH CH NH in which R is an aliphatic group having from six to23 carbon atoms. The diamines may be obtained from fatty acids ofnatural fats or oils, such as tallow, soybean oil, cottonseed oil,coconut oil, or from fractions of these natural acid mixtures, saturatedor unsaturated. Also, the diamines may be obtained from sources such asunsaturated acids and olefins. The long chain hydrocarbon radical may bestraight chain or branched chain and saturated or unsaturated. Thediamine may be alkoxylated with a compound such as ethylene or propyleneoxide, either adding a ,B-hydroxyalkyl group or a higher adduct thereof,preferably from about 3 to 20 moles of alkylene oxide per mole ofdiamine.

Other polyamines may be utilized in this invention. Particularlysuitable are tri amines and tetra amines. Specifically, tn aminesproduced by monocyanoethylation of any of the above-mentioned diaminesfollowed by reduction of the nitrile group to an amine are suitable foruse in this invention. Likewise, tetra amines may be produced bydicyanoethylation of diamines, and particularly diamines having twoprimary amino groups such as aminostearylamine.

The plant hormones occur generally in the form of carboxylic acids.Examples are 2,4-dichlorophenoxyacetic acid 2,4,5-trichlorophenoxyaceticacid, methylchlorophenoxyacetic acid chlorinated benzoic acid,dichloropropionic acid, B-indolylacetic acid,anaphthaleneacetic acid,indolylbutyric acid, indolylpropionic acid, phenylacetic acid,fluoroacetic acid,

2,5-dichloro-3-nitro benzoic acid, 3-amino-2,5- dichloro benzoic acid,and 3,6-endoxohexahydrophthalic acid.

The reaction between the amine and the carboxylic acid may be carriedout in any suitable manner. For example, the two substances may be mixedin a solvent and warmed until a homogeneous solution is obtained, andthen cooled until precipitation of the salt is complete, after which itmay be filtered and dried.

The resulting salts are viscous liquids which may be then dissolved inorganic solvents or emulsified to form oil-in-water emulsions, and thecomposition applied by spraying or by other suitable means to the areaabout the plants, etc.

The following specific examples are illustrative of our invention.

EXAMPLE I Thirty six grams of N-oleyl trimethylenediamine and 22.1 gramsof 2,4-dichlorophenoxy acetic acid were mixed together and warmed untila clear solution was obtained. When cooled, the viscous product obtainedwas a 2,4-dichlorophenoxyacetic acid mono salt of N oleyltrimethylenediamine.

EXAMPLE H Thirty six grams-of N-tallow trimethylenediamine and 22.1grams of 2,4-dichlorophenoxyacetic acid were mixed together in ethylacetate and warmed until clear. The product, 2,4-dichlorophenoxyaceticacid mono salt of N-tallow trimethylenediamine was cooled, filtered anddried.

EXAMPLE III Thirty six grams of N-tallow trimethylenediamine and 44.2grams of 2,4-dichlorophenoxyacetic acid were mixed together in 100 gramsof benzene. The mixture was warmed until solution was obtained, thencooled, filtered and dried. The product was 2,4- dichlorophenoxyaceticacid di salt of N-tallow trimethylenediamine.

EXAMPLE IV In like fashion, the following plant hormone carboxylic acidsalts of polyamines were prepared:

2,4-dichlorophenoxyacetic acid mono and di salts of N-soyatrimethylenediamine. 2,4,5-trichlorophenoxyacetic acid mono and di saltsof N-oleyl trimethylenediamine. 2,4,5-trichlorophenoxyacetic acid monoand di salts of N-soya trimethylenediamine. 2,4,5-trichlorophenoxyaceticacid mono and di salts of N-tallow trimethylenediamine.2,4-dichlorophenoxyacetic acid di salt of N-oleyl trimethylenediamine.Dimethyl arsenic acid di salt of N-tallow trimethylenediamine(ethoxylated with 3 ethylene oxide). 2,5-dichloro-3-nitr0benzoic acidmono salt of aminomethylstearylamine. 2,4-dichlorophenoxyacetic acid trisalt of N-tallow- N-('y-aminopropyl)-trimethylenediamine.3-amino-2,S-dichlorobenzoic acid salt aminomethylstearylamine.3,6-endoxohexahydrophthalic acid mono and di salts ofaminomethylstearylamine. 2,4-dichlorophenoxyacetic acid mono and disalts of aminomethylstearylamine. 3-amino-2,S-dichlorobenzoic acid disalt of N-tallow trimethylenediamine (ethoxylated with 3 moles ethyleneoxide). 2,5-dichloro-3-nitrobenzoic acid di salt of N-tallowtrimethylenediamine (ethoxylated with 3 moles ethylene oxide).3,6-endoxohexahydrophthalic acid salt of N-(C -C sec-alkyl)trimethylenediamine. 2,4-dichlorophenoxyacetic acid salt of N-(l-hendecyldodecyl) N,N'-diethyl trimethylenediamine.

2,4-dichlorophenoxyacetic acid salt of N-( lmethyloctadecyl) N,N-diethyltrimethylenediamine.

2,4-dichlorophenoxyacetic acid mono and di salts of N-(xylylstearyl)trimethylenediamine.

3,6-endoxohexahydrophthalic acid mono and di salts of N-(xylylstearyl)trimethylenediamine.

3,6-endoxohexahydrophthalic acid mono and di salts of N,N,N',Ntetramethyl aminomethylstearylamine.

2,4-dichlorophenoxyacetic acid mono and di salts of N,N,N, N tetramethylaminomethylstearylamine.

3,6-endoxohexahydrophthalic acid mono and di salts of N-(phenylbehenyl)trimethylenediamine.

2,4-dichlorophenoxyacetic acid mono and di salts of N -(phenylbehenyl)trimethylenediamine.

a ,a-dichloropropionic acid mono and di salts of N- (C C sec-alkyl)trimethylenediamine.

2,4-dichlorophenoxyacetic acid tn salt of N-oleyl-N'-(y-aminopropyl)-trimethylenediarnine.

Bfi-dichloropropionic acid mono and di salts of N- (C C sec-alkyl)trimethylenediamine.

a,a-dichloropropionic acid mono and di salts of N- (C C sec-alkyl)trimethylenediamine(ethoxylated with 3 moles ethylene oxide).

a,a-dichloropropionic acid mono and di salts of N- oleyltrimethylenediamine.

a,a-dichloropropionic acid mono and di salts of N- tallowtrimethylenediamine (ethoxylated with 10 moles ethylene oxide).

EXAMPLE V 2,4-dichlorophenoxyacetic acid mono salt of N-oleyltrimethylenediamine prepared as described in Example 1 was dissolved inkerosene and applied at the rate of 8 to 14 pounds of active ingredientsper acre to a rightof-way adjoining cotton, the composition beingapplied as a spray. The composition was effective against sumac,sassafras, as well as weeds, and while the right-ofway was rendered freeof weeds up to the fence ad jacent the cotton plants, no damage to thecotton was found.

EXAMPLE VI brought about a degree of lead modification, indicatingsubstantial volatility.

EXAMPLE VII 2,4-dichlorophenoxyacetic acid mono salt of N-oleyltrimethylenediamine prepared as described in Example I was applied to agolf course for the elimination of weeds. About two quarts of thecomposition in an oilin-water emulsion was applied per acre andsuccessfully eliminated weeds while leaving a flourishing grass turf.

EXAMPLE Vlll Diamine salts of plant hormone carboxylic acids wereapplied to various crops and weeds to ascertain their selectiveherbicidal action. Table I shows the results of pre-emergenceapplication of chemical.

Diarnine salts of plant hormone carboxylic acids were applied todifferent crops and weeds to illustrate their efiective and selectiveherbicidal action. Table II EXAMPLE Xl One mole ofN,N'-('y-aminopropyl)-aminomethylstearylamine (50 percent active inisopropanol) was warmed to about 70 C and four moles of 2,4-

5 shows the results f post emergence application ofdichlorophenoxyacetic acid were added slowly. During chemica1 thisaddition the temperature was maintained at about TABLE I Injury ratingWoods Pounds per S y- Sugor Spin- String Cucum- Brood- Ghemjcal acreCorn boon Cotton boot och Wheat boon bor lent Gr2,fi-diehloro-B-nitrobenzoic acid mono salt of 5 lg 12aminomethylstearylamine n 10 2 2,4-dichlorophenoxyacetic acid mono saltof 9 6 aminomethylstearylamine 7 8 5 2,4-dichlorophenoxyacetic acid d1salt of amino- 9 3 methylstearylamine 10 5 3amino-2,5-dichlorobenzoicacid di salt of N-sec- 10 10 tridecyl trimethylenediamine (ethoxylated 97 with 3 moles ethylene oxide) 2 4 2,5-dichloro-a-nitrobenzoic acid disalt of N-sec- 10 10 tridecyl trimethylenediamine (ethoxylatcd 9 8 with3 moles ethylene oxide) 3,6-ondoxohcxohydrophthalic acid mono salt of 1010 10 10 4.4 N-(U C sec-alkyl) trimethylenediamine. 10 9-D 10 6 9Rating:

=No injury. 1=Slight injury. =Moderate injury. 9=Very heavy injury.=Plants dead. a iR lisl-w.

TABLE II Injury rating weeds Pounds per Soy- Sugar Red Soroadca acreCorn bean beet beet Wheat ghurn Cotton leaf Grass3,6-endoxohexahydrophthalic acid mono salt of N-(cu-cu 4 3 8.5 0 6 1osec-alkyl) trimethyl n diamine 8 8 9. 5 4, 5 5 5 10 52,4-dich1orophenoxyacetic acid di salt of aminomethylstearyl 0. 5 0 9-H4; .11 5 0 amine 1 2 10 10 10 0. 5 10 5 0 *Ratings same as Table I withaddition oi: H=Horrnona1 curvature.

EXAMPLE X Diamine salts of plant hormone carboxylic acids were appliedpre-emergence to a soybean crop to ascertain germination and injury tothe soybean crop and weed control. Results are shown below in Table III.

trimethylenediamine Ratings same as Table l to C and agitation wasprovided by a nitrogen sparger until the reaction was complete. Theproduct was the 2,4dichlorophenoxyacetic acid tetra salt ofN,N'-('y-aminopropyl)-aminomethylstearylamine.

The terms oleyl, soya, coco and tallow refer to mixtures of long chainhydrocarbon radicals derived from oleic acid and fatty acids derivedfrom soybean, coconut and tallow sources respectively.

While in the foregoing specification we have set forth illustrativeembodiments in considerable detail for the purpose of explaining theinvention, it will be understood that such detail or details may bevaried widely by those skilled in the art without department from thespirit of our invention.

We claim:

1. As a herbicidal agent, a plant hormone carboxylic acid salt of atrimethylenediamine selected from the group consisting of N-oleyl,N-soya, N-coco and N-tallow trimethylenediamine.

2. The compound of claim 1 in which the plant hormone is2,4-dichlorophenoxyacetic acid.

3. The compound of claim 1 in which the plant hormone is2,4,5-trichlorophenoxyacetic acid.

4. As an herbicidal agent, the N-oleyl trimethylenediamine salt of2,4-dichlorophenoxyacetic acid.

5. As an herbicidal agent, the N-oleyl trimethylenediamine salt of2,4,5-trichlorophenoxyacetic acid.

2. The compound of claim 1 in which the plant hormone is2,4-dichlorophenoxyacetic acid.
 3. The compound of claim 1 in which theplant hormone is 2,4,5-trichlorophenoxyacetic acid.
 4. As an herbicidalagent, the N-oleyl trimethylenediamine salt of 2,4-dichlorophenoxyaceticacid.
 5. As an herbicidal agent, the N-oleyl trimethylenediamine salt of2,4,5-trichlorophenoxyacetic acid.